Acetic Acid → Isolongifolanone- parent

HRID 2198064Notes

Reaction equation

HRID 2198064 reaction equation
[CH3:1][C:2]1([CH3:15])[CH:8]2[CH:9]3[CH2:12][CH2:13][CH:7]2[C:6]([CH3:14])([C:10]3=[CH2:11])[CH2:5][CH2:4][CH2:3]1.C(O)(=[O:18])C>C1(C)C=CC=CC=1>[CH3:9][C:10]1([CH3:11])[CH:12]2[C:3]3([CH2:14][CH:6]1[CH2:5][CH2:4]3)[C:2]([CH3:15])([CH3:1])[CH2:8][CH2:7][C:13]2=[O:18]

Participants

4

Reactant 2

HCID 176Acetic AcidHCID 2891514,8,8-Trimethyl-9-methylidenedecahydro-1,4-methanoazulene

Product 1

HCID 90978Isolongifolanone- parent

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
20 °C

Procedure

A four neck flask of 2 L was charged with 500 g of longifolene and 250 ml of acetic acid, and 250 ml of a boron trifluoride diethyl ether complex was dropwise added thereto in 4 hours while stirring at 20° C. to carry out isomerization reaction. This reaction mixture was washed with ice and water, a saturated sodium hydrogencarbonate aqueous solution and a saturated saline solution and refined by distillation, and after refined by distillation, it was mixed with 1800 ml of methylene chloride and 900 ml of a 0.5 mole/L sodium hydrogencarbonate aqueous solution, followed by slowly adding thereto 400 g of 3-chloroperbenzoic acid at 10° C. or lower. After finishing the reaction, the reaction mixture was washed with a 1 mole/L sodium hydroxide aqueous solution and water and concentrated under reduced pressure to obtain a crude product. It was dissolved in 3 L of toluene, and 260 ml of a boron trifluoride diethyl ether complex was slowly dropwise added thereto at 5° C. or lower. After finishing the reaction, the reaction mixture was washed with water and refined by distillation to thereby obtain 270 g of 1,1,5,5-tetramethylhexahydro-2H-2,4a-methano-naphthalene-8-one. This was dropwise added to 640 ml of a 2.1 mole/L methyl lithium/diethyl ether solution at 5° C. or lower to carry out alkylation, and after finishing the reaction, the reaction mixture was washed with a saturated ammonium chloride aqueous solution and water. This reaction product was charged into an autoclave of 1 L together with 30 g of the nickel/diatomaceous earth catalyst for hydrogenation (N-113, manufactured by Nikki Chemical Co., Ltd.) to carry out dehydration hydrogenation (hydrogen pressure: 6 MPa·G, reaction temperature: 250° C., reaction time: 6 hours).

Workup

  1. additionwas dropwise added
  2. customto carry out isomerization reaction
  3. washThis reaction mixture was washed with ice and water
  4. distillationa saturated sodium hydrogencarbonate aqueous solution and a saturated saline solution and refined by distillation
  5. distillationafter refined by distillation, it
  6. additionwas mixed with 1800 ml of methylene chloride and 900 ml of a 0.5 mole/L sodium hydrogencarbonate aqueous solution
  7. additionby slowly adding
  8. customat 10° C.
  9. customthe reaction
  10. washthe reaction mixture was washed with a 1 mole/L sodium hydroxide aqueous solution and water
  11. concentrationconcentrated under reduced pressure
  12. customto obtain a crude product
  13. addition260 ml of a boron trifluoride diethyl ether complex was slowly dropwise added
  14. customat 5° C.
  15. customthe reaction
  16. washthe reaction mixture was washed with water and refined by distillation

Sources & evidence

ORD record
ord-9f23337cbf2344f793964c9d6aabc51d
Source dataset
uspto-grants-2012_12
Patent number
US08338653B2

Reaction notes

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